JP6439612B2 - Epoxy resins, compositions, cured products, and electrical / electronic components - Google Patents

Description

  The present invention includes an epoxy resin having low melt viscosity, low softening point, excellent handling properties, low hydrolyzable chlorine and excellent electrical characteristics, and this epoxy resin, including blocking resistance, heat resistance, water absorption, and elasticity at high temperatures. The present invention relates to an epoxy resin composition and a cured product excellent in rate. The present invention also relates to an electrical / electronic component comprising the epoxy resin composition.

Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, heat resistance, electrical properties, etc., and are used in a wide range of fields such as adhesives, paints, and electrical / electronic materials. ing. In the field of electrical / electronic materials, for example, cresol novolac type epoxy resins are generally used for semiconductor sealing materials.
With the remarkable development of the electronic industry in recent years, the requirements for heat resistance and water absorption required for electronic devices have become increasingly severe. The epoxy resin described in Example 2 described in Patent Document 1 has a Tg of 176 ° C. from the viewpoint of heat resistance and 0.93% from the viewpoint of water absorption, which is higher in heat resistance and lower water absorption than conventional ortho-cresol novolac type epoxy resins. However, it is still not satisfactory in terms of heat resistance and water absorption.

Japanese Patent Laid-Open No. 7-292066

  According to the detailed study by the present inventors, even an epoxy resin described in Patent Document 1 has sufficiently good heat resistance, water absorption, elastic modulus at high temperature, etc. A resin composition has not been obtained. Accordingly, the present invention includes an epoxy resin having low melt viscosity, softening point and excellent handling properties, low hydrolyzable chlorine and excellent electrical characteristics, and this epoxy resin, including blocking resistance, heat resistance, water absorption, and high temperature. An object of the present invention is to provide an epoxy resin composition, a cured product, and an electric / electronic component having an excellent elastic modulus.

As a result of intensive studies by the present inventors to solve the above-mentioned problems, an epoxy resin composition comprising an epoxy resin obtained from a phenol resin having a specific n number of a specific skeleton, an epoxy resin, and a curing agent has the above problems. It has been found to solve. That is, the gist of the present invention resides in the following [1] to [10].
[1] The following formula (1)

(In the above formula (1), n represents an average value and takes a value of 0.01 to 0.8.)
An epoxy resin obtained by converting a phenol resin represented by
[2] The epoxy resin according to [1], wherein the epoxy equivalent is 161 to 191 g / equivalent.
[3] The epoxy resin according to [1] or [2], which has a melt viscosity at 150 ° C. of 3.5 Pa · s or less.
[4] The epoxy resin according to any one of [1] to [3], wherein hydrolyzable chlorine is 770 ppm or less.
[5] The epoxy resin according to any one of [1] to [4], which has a softening point of 48 to 70 ° C.
[6] An epoxy resin composition comprising 0.01 to 1000 parts by weight of a curing agent with respect to 100 parts by weight of the epoxy resin according to any one of [1] to [5].
[7] The epoxy resin composition according to [6], wherein the curing agent is at least 1 selected from the group consisting of a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, and an amide curing agent. [8] The epoxy resin composition according to [6] or [7], further comprising an epoxy resin different from the epoxy resin according to any one of [1] to [5].
[9] A cured product obtained by curing the epoxy resin composition according to any one of [6] to [8].
[10] An electrical / electronic component obtained by curing the epoxy resin composition according to any one of [6] to [8].

  According to the present invention, the melt viscosity, softening point is low, the handling property is excellent, the hydrolyzable chlorine is low and the electrical property is low, and this epoxy resin is included, blocking resistance, heat resistance, water absorption, at high temperature An epoxy resin composition, a cured product, and an electric / electronic component having an excellent elastic modulus are provided. Moreover, since the epoxy resin composition of this invention has said effect, it can apply especially useful to the field | area of a semiconductor sealing material.

Embodiments of the present invention will be described in detail below, but the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following description unless it exceeds the gist. Absent. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression.
〔Epoxy resin〕
The epoxy resin of the present invention is obtained by converting a phenol resin of the following formula (1) into an epoxy resin. The epoxy resin of the present invention has an effect that the melt viscosity and softening point are low and the handling property is excellent, the hydrolyzable chlorine is low and the electrical property is particularly excellent.

  The reason why the epoxy resin has these effects is not clear, but the reason why the melt viscosity and the softening point are low is that the n number of the raw material phenol of the epoxy resin represented by the following formula (1) is low and the molecular weight is low. The reason why the hydrolyzable chlorine is low is presumed that the n number of the raw material phenol of the epoxy resin represented by the following formula (1) is low and the polymer component is not inhibited by alkali treatment by the hydrolyzable chlorine reduction reaction. Is done.

(In the above formula (1), n represents an average value and takes a value of 0.01 to 0.8.)
<Chemical structure>
In said Formula (1), n shows an average value and takes the value of 0.01-0.8. When the value of n is less than 0.01, when it is set as a cured epoxy resin, the blocking resistance is deteriorated and its use becomes difficult, which is not preferable. On the other hand, when the value of n exceeds 0.8, the softening point and the melt viscosity at 150 ° C. are increased, which is not preferable from the viewpoint of handleability. In addition, the content of hydrolyzable chlorine is increased and the electrical characteristics are deteriorated.
The value of n is preferably 0.06 as the lower limit and 0.7 as the upper limit.

<Physical properties / characteristics>
[Epoxy equivalent]
The epoxy resin of the present invention has an epoxy equivalent of 161 to 191 g / equivalent. 161 to 185 g / equivalent is preferable from the viewpoint of reducing hydrolyzable chlorine, and 166 to 185 g / equivalent is more preferable from the viewpoint of increasing blocking resistance. From the viewpoint of lowering the melt viscosity at 150 ° C., it is particularly preferably 166 to 179.
In the present invention, “epoxy equivalent” is defined as “the mass of an epoxy resin containing one equivalent of an epoxy group” and can be measured according to JIS K7236.

[Hydrolyzable chlorine content]
The epoxy resin of the present invention preferably has a hydrolyzable chlorine content (hereinafter sometimes referred to as “hydrolyzable chlorine content”) of 770 ppm or less. Moreover, from a viewpoint of making an electrical property more favorable, it is more preferable that it is 680 ppm or less, and it is especially preferable that it is 590 ppm or less from a viewpoint of reducing the melt viscosity at 150 degreeC.

As a method for measuring the amount of hydrolyzable chlorine, for example, about 0.5 g of epoxy resin is dissolved in 20 ml of dioxane, refluxed with 5 ml of 1N KOH / ethanol solution for 30 minutes, and then titrated with 0.01N silver nitrate solution. The method of quantifying by is mentioned.
In order to reduce the amount of hydrolyzable chlorine in the epoxy resin, the epoxy resin may be purified by a reaction between the epoxy resin and a strong alkali in the method for producing an epoxy resin described later.

[Melt viscosity]
The epoxy resin of the present invention preferably has a melt viscosity at 150 ° C. of 3.5 Pa · s or less from the viewpoint of handleability, and from the viewpoint of improving the handleability, the melt viscosity is 2. It is 8 Pa · s or less and particularly preferably 2.1 Pa · s or less.
In the present invention, the “melt viscosity” is a viscosity measured at a rotational speed of 750 rpm by melting an epoxy resin on a hot plate of a cone plate viscometer (manufactured by Tokai Yagami Co., Ltd.) adjusted to 150 ° C. .

[Softening point]
The epoxy resin of the present invention preferably has a softening point of 70 ° C. or lower from the viewpoint of handleability, and from the viewpoint of improving the handleability, this softening point is 66 ° C. or lower and 61 ° C. or lower. It is particularly preferable that On the other hand, it is preferable that it is 48 degreeC or more from a viewpoint of blocking resistance, and it is more preferable that it is 50 degreeC or more. In the present invention, the “softening point” can be measured according to JIS K7234.

[Method for producing epoxy resin]
Although there is no restriction | limiting in particular about the manufacturing method of an epoxy resin, For example, the manufacturing method by the one-step method demonstrated below, the manufacturing method by a two-step method, the manufacturing method via an allylation reaction, etc. are mentioned. These methods are described in detail below.
[Production method by one-step method]
The epoxy resin according to another embodiment of the present invention is obtained by reacting a phenol compound represented by the following formula (1) with epihalohydrin.

(In the above formula (1), n represents an average value and takes a value of 0.01 to 0.8.)
When producing an epoxy resin by a one-step method, at least a phenol compound represented by the above formula (1) and an epihalohydrin are used as raw materials, but a polyvalent hydroxy compound other than the phenol compound represented by the formula (1) (In the present invention, it may be referred to as “other polyvalent hydroxy compound”) may be used in combination. However, from the viewpoint of enhancing the effect of the present invention, the proportion of the phenol compound represented by the formula (1) is preferably 30 mol% or more, more preferably 50 mol, based on the total amount of the entire polyvalent hydroxy compound used as a raw material. It is more than mol%, more preferably more than 80 mol%. Moreover, the upper limit is 100 mol%, Most preferably, it is 100 mol%. The “polyhydric hydroxy compound” in the present invention is a general term for dihydric or higher phenol compounds and dihydric or higher alcohols.

  Other polyhydroxy compounds include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, bisphenol AF, hydroquinone, resorcin, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac Resin, cresol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolak resin, naphthol novolak resin, brominated bisphenol A, brominated phenol novolak resin, etc. Polyhydric phenols (however, phenolation represented by the formula (1)) And polyphenol resins obtained by condensation reactions of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glyoxal, and condensation reactions of xylene resins with phenols. Polyphenol resins obtained, various phenol resins such as heavy oil or co-condensation resin of pitches, phenols and formaldehyde, ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, Chain aliphatic diols such as 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol; cyclohexanediol, cyclodecanediol, etc. Of cycloaliphatic diols; Ether glycol, polyoxyethylene trimethylene ether glycol, polyalkylene ether glycols such as polypropylene ether glycol, and the like. Among these, phenol novolak resin, phenol aralkyl resin, polyhydric phenol resin obtained by condensation reaction of phenol and hydroxybenzaldehyde, biphenyl aralkyl resin, naphthol aralkyl resin, ethylene glycol, trimethylene glycol, propylene glycol, Chain aliphatic diols such as 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, Cycloaliphatic diols such as cyclohexanediol and cyclodecanediol, and polyalkylene ether glycols such as polyethylene ether glycol, polyoxytrimethylene ether glycol, and polypropylene ether glycol Le, and the like can be mentioned.

A compound having two or more hydroxyl groups used as a raw material is usually 0 per equivalent of the hydroxyl groups.
. A uniform solution is obtained by dissolving in 8 to 20 equivalents, preferably 0.9 to 15 equivalents, more preferably 1.0 to 10 equivalents of epihalohydrin. It is preferable that the amount of epihalohydrin is not less than the above lower limit because the high molecular weight reaction can be easily controlled and an appropriate melt viscosity can be obtained. On the other hand, when the amount of epihalohydrin is less than or equal to the above upper limit, production efficiency tends to improve, which is preferable. In addition, as epihalohydrin in this reaction, epichlorohydrin or epibromohydrin is usually used.

  Next, while stirring the solution, it is usually 0.5 to 2.0 equivalents, more preferably 0.7 to 1.8 equivalents, still more preferably 0.9 to 1.6 equivalents per equivalent of hydroxyl group of the raw material. An amount of alkali metal hydroxide corresponding to an equivalent amount is added as a solid or an aqueous solution, and reacted. It is preferable for the amount of the alkali metal hydroxide to be not less than the above lower limit because the unreacted hydroxyl group and the generated epoxy resin are difficult to react and the high molecular weight reaction can be easily controlled. Further, it is preferable that the amount of the alkali metal hydroxide is not more than the above upper limit value because impurities due to side reactions are hardly generated. As the alkali metal hydroxide used here, sodium hydroxide or potassium hydroxide is usually mentioned.

  This reaction can be performed under normal pressure or reduced pressure, and the reaction temperature is preferably 40 to 150 ° C, more preferably 60 to 100 ° C, and still more preferably 80 to 100 ° C. It is preferable for the reaction temperature to be equal to or higher than the above lower limit because the reaction can easily proceed and the reaction can be easily controlled. Further, it is preferable that the reaction temperature is not more than the above upper limit because the side reaction is unlikely to proceed, and in particular, chlorine impurities are easily reduced.

  In the reaction, the reaction liquid is azeotroped while maintaining a predetermined temperature as required, the condensed liquid obtained by cooling the vaporized vapor is separated into oil / water, and the oil component excluding moisture is returned to the reaction system. To dehydrate. The addition of alkali metal hydroxide is preferably 0.1 to 8 hours, more preferably 0.1 to 7 hours, and still more preferably 0.5 to 6 hours in order to suppress a rapid reaction. Add intermittently or continuously. It is preferable for the addition time to be equal to or more than the above lower limit because the reaction can be prevented from proceeding rapidly and the reaction temperature can be easily controlled. It is preferable for the addition time to be less than or equal to the above upper limit because chlorine impurities are less likely to be generated, and from the viewpoint of economy. The total reaction time is usually 1 to 15 hours. After completion of the reaction, the insoluble by-product salt is removed by filtration or removed by washing with water, and then the unreacted epihalohydrin is removed by distillation under reduced pressure to obtain the desired epoxy resin.

In this reaction, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; 2-ethyl Catalysts such as imidazoles such as -4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; phosphines such as triphenylphosphine may be used.

  Furthermore, in this reaction, alcohols such as ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and ethylene glycol dimethyl ether; glycol ethers such as methoxypropanol; aprotic such as dimethyl sulfoxide and dimethylformamide An inert organic solvent such as a polar solvent may be used.

In addition, when it is necessary to reduce the total chlorine content of the epoxy resin obtained as described above, a purified epoxy resin having a sufficiently reduced total chlorine content can be obtained by reprocessing. That is, the crude epoxy resin is redissolved in an inert organic solvent such as isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dioxane, methoxypropanol, dimethyl sulfoxide, and the alkali metal hydroxide is added to the solid or aqueous solution. The temperature is preferably 30 to 120 ° C., more preferably 40 to 110 ° C., still more preferably 50 to 100 ° C., preferably 0.1 to 15 hours, more preferably 0.3 to 12 hours, still more preferably 0.00. After re-ringing reaction for 5 to 10 hours, excess alkali metal hydroxide or by-product salt is removed by a method such as washing with water, and further the organic solvent is distilled off under reduced pressure and / or steam distillation to hydrolyze. It is possible to obtain an epoxy resin with a reduced amount of reactive halogen. It is preferable that the reaction temperature is not less than the above lower limit and the reaction time is not less than the above lower limit because the re-ring closure reaction easily proceeds. Moreover, since reaction temperature is below the said upper limit and reaction time is below the said upper limit, since reaction is easy to control, it is preferable.

[Production method by oxidation of allyl compound]
As one of the manufacturing methods of the epoxy resin of this invention, an allyl group is introduce | transduced by the allylation reaction with respect to the phenol compound represented by said Formula (1), and it is made an allyl compound, and also oxidation reaction with respect to this allyl group The method of obtaining an epoxy resin by doing is mentioned. As an example of such a production method, JP2012-213716A, JP2011-225711A, JP2012-092247A, except that the phenol compound represented by the formula (1) is used as a raw material. Can be produced by the methods disclosed in Japanese Unexamined Patent Publication No. 2012-111858.

[Epoxy resin composition]
The epoxy resin composition of the present invention contains at least the above-described epoxy resin of the present invention and a curing agent. Moreover, the epoxy resin composition of this invention can mix | blend suitably another epoxy resin, a hardening accelerator, an inorganic filler, a coupling agent, etc. as needed. The epoxy resin composition of the present invention is excellent in heat resistance, water absorption, and elastic modulus at heat, and gives a cured product that sufficiently satisfies various physical properties required for various applications.

<Curing agent>
In the epoxy resin composition of this invention, when other epoxy resins mentioned later are contained, it is preferably 0.1 to 200 parts by weight with respect to 100 parts by weight of the total epoxy resin component as a solid content. Further, it is more preferably 100 parts by weight or less, and still more preferably 80 parts by weight or less. In the present invention, the “solid content” means a component excluding the solvent, and includes not only a solid epoxy resin but also a semi-solid or viscous liquid material. The “total epoxy resin component” means the total of the epoxy resin of the present invention and other epoxy resins described later.
In this invention, a hardening | curing agent shows the substance which contributes to the crosslinking reaction and / or chain length extension reaction between the epoxy groups of an epoxy resin. In the present invention, even if what is usually called a “curing accelerator” is a substance that contributes to a crosslinking reaction and / or chain extension reaction between epoxy groups of an epoxy resin, it is regarded as a curing agent. To do.

[Phenolic curing agent]
The epoxy resin composition of the present invention contains a phenolic curing agent. By including the phenolic curing agent, the epoxy resin composition of the present invention can obtain excellent heat resistance, low linear expansion, and adhesiveness.

The phenolic curing agent used in the present invention is not limited as long as it is a phenolic curing agent. Specific examples include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcin, methyl resorcin, biphenol, and tetramethyl. Biphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolak resin, naphthol novolak Various polyphenols such as resin, brominated bisphenol A, brominated phenol novolac resin, Polyphenols obtained by condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glyoxal, polyhydric phenol resins obtained by condensation reaction of xylene resin and phenols , Co-condensation resin of heavy oil or pitches, phenols and formaldehyde, phenol / benzaldehyde / xylylene dimethoxide polycondensate, phenol / benzaldehyde / xylylene dihalide polycondensate, phenol / benzaldehyde 4,4 ' -Various phenol resins such as dimethoxide biphenyl polycondensate and phenol / benzaldehyde / 4,4′-dihalide biphenyl polycondensate. These phenol compounds may be used alone or in combination of two or more.

(However, in the above formulas (2) to (7), k _{1 to} k ₆ each represents a number of 0 or more.)

(However, in the above formulas (8) and (9), k ₇ , k ₈ , l ₁ , and l ₂ each represent a number of 1 or more.)
The phenolic curing agent is preferably 0.1 to 200 parts by weight with respect to 100 parts by weight of the total epoxy resin component as a solid content. Further, it is more preferably 100 parts by weight or less, and still more preferably 80 parts by weight or less. Each component of the phenolic curing agent listed above may be used after mixing in advance to prepare a mixed curing agent, or when mixing each component of the epoxy resin composition, each component of the curing agent may be used. They may be added separately and mixed at the same time.

[Amine curing agent]
Examples of amine curing agents (excluding tertiary amines) include aliphatic amines, polyether amines, alicyclic amines, aromatic amines and the like. Aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine and the like are exemplified. Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like. Cycloaliphatic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino). Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like. Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4 -Toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) ethylamine Diaminodiethyldi Examples thereof include methyldiphenylmethane and α, α′-bis (4-aminophenyl) -p-diisopropylbenzene.

  The amine curing agents mentioned above may be used alone or in combination of two or more in any combination and mixing ratio. Moreover, it is preferable to use an amine hardening | curing agent so that it may become the range of 0.8-1.5 by the equivalent ratio of the functional group in a hardening | curing agent with respect to the epoxy group in an epoxy resin. Within this range, unreacted epoxy groups and functional groups of the curing agent are unlikely to remain, which is preferable.

Examples of the tertiary amine include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol. .
The tertiary amines mentioned above may be used alone or in combination of two or more in any combination and blending ratio. Moreover, it is preferable to use a tertiary amine so that it may become the range of 0.8-1.5 in the equivalent ratio of the functional group in the hardening | curing agent with respect to the epoxy group in an epoxy resin. Within this range, unreacted epoxy groups and functional groups of the curing agent are unlikely to remain, which is preferable.

[Acid anhydride curing agent]
The epoxy resin composition of the present invention preferably uses an acid anhydride curing agent from the viewpoint of heat resistance. Examples of the acid anhydride curing agent include acid anhydrides and modified acid anhydrides.
Examples of acid anhydrides include phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, dodecenyl succinic acid anhydride, polyadipic acid anhydride, polyazelinic acid anhydride, polysebacic acid Anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride , Methyl hymic acid anhydride, tetrahydrophthalic acid anhydride, trialkyltetrahydrophthalic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bis trimellitate dianhydride, het acid anhydride , Najit Acid anhydride, methyl nadic acid anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy- Examples include 1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and the like.

  Examples of modified acid anhydrides include those obtained by modifying the above acid anhydride with glycol. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; polyether glycols such as polyethylene glycol, polypropylene glycol, and potassium tetramethylene ether glycol. Is mentioned. Further, a copolymer polyether recall of two or more kinds of these and / or polyether glycol can also be used.

In the modified product of acid anhydride, it is preferable to modify with 0.4 mol or less of glycol with respect to 1 mol of acid anhydride. When the modification amount is not more than the above upper limit, the viscosity of the epoxy resin composition does not become too high, the workability tends to be good, and the rate of the curing reaction with the epoxy resin also tends to be good. .
The acid anhydride curing agents listed above may be used alone or in combination of two or more in any combination and blending amount. When an acid anhydride curing agent is used, it is preferably used so that the equivalent ratio of the functional group in the curing agent to the epoxy group in the epoxy resin is in the range of 0.8 to 1.5. Within this range, unreacted epoxy groups and functional groups of the curing agent are unlikely to remain, which is preferable.

[Amide-based curing agent]
It is preferable to use an amide-based curing agent as the curing agent from the viewpoint of improving heat resistance and the like. Use of an amide type epoxy resin curing agent as the epoxy resin curing agent is preferable from the viewpoint of improving the heat resistance of the resulting epoxy resin composition. Examples of the amide-based curing agent include dicyandiamide and derivatives thereof, and polyamide resins.
The phenolic curing agents listed above may be used alone or in a combination of two or more in any combination and ratio. Moreover, it is preferable to use an amide type hardening | curing agent in 0.1-20 weight% with respect to the sum total of all the epoxy resin components and amide type hardening | curing agents as solid content in an epoxy resin composition.

[Imidazoles]
It is preferable to use imidazoles as the curing agent from the viewpoint of sufficiently proceeding the curing reaction and improving the heat resistance. Examples of imidazoles include 2-phenylimidazole, 2-ethyl-4 (5) -methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s -Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-tri Azine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and an epoxy resin and the above imidazoles Examples include adducts. In addition, since imidazoles have catalytic ability, they can generally be classified as curing accelerators described later, but in the present invention, they are classified as curing agents.
The imidazoles listed above may be used alone or in combination of two or more in any combination and ratio. Moreover, it is preferable to use imidazole in 0.1-20 weight% with respect to the sum total of all the epoxy resin components and imidazoles as solid content in an epoxy resin composition.

[Other curing agents]
In the epoxy resin composition of the present invention, other curing agents can be used in addition to the curing agent. Other curing agents that can be used in the epoxy resin composition of the present invention are not particularly limited, and any of those generally known as curing agents for epoxy resins can be used. These other curing agents may be used alone or in combination of two or more.

<Other epoxy resins>
The epoxy resin composition of the present invention can further contain other epoxy resins in addition to the epoxy resin of the present invention. By including other epoxy resins, the heat resistance, stress resistance, moisture absorption resistance, flame retardancy, and the like of the epoxy resin composition of the present invention can be improved.
Other epoxy resins that can be used in the epoxy resin composition of the present invention are all epoxy resins other than the epoxy resin of the present invention. Specific examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, Bisphenol AD type epoxy resin, hydroquinone type epoxy resin, methyl hydroquinone type epoxy resin, dibutyl hydroquinone type epoxy resin, resorcin type epoxy resin, methyl resorcin type epoxy resin, biphenol type epoxy resin, tetramethyl biphenol type epoxy resin, tetramethylbisphenol F Type epoxy resin, dihydroxydiphenyl ether type epoxy resin, epoxy resin derived from thiodiphenols, dihydroxynaphthalene type epoxy resin, dihydroxyanthracene Epoxy resin, dihydroxydihydroanthracene type epoxy resin, epoxy resin derived from dihydroxystilbenes, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, naphthol novolak type epoxy resin, phenol aralkyl type epoxy resin Derived from naphthol aralkyl epoxy resin, biphenyl aralkyl epoxy resin, terpene phenol epoxy resin, dicyclopentadiene phenol epoxy resin, epoxy resin derived from phenol / hydroxybenzaldehyde condensate, phenol crotonaldehyde condensate Epoxy resins, epoxy resins derived from phenol / glyoxal condensates, heavy oils or Epoxy resins derived from co-condensation resins of phenols, phenols and formaldehyde, epoxy resins derived from diaminodiphenylmethane, epoxy resins derived from aminophenol, epoxy resins derived from xylenediamine, methylhexa Examples thereof include an epoxy resin derived from hydrophthalic acid, an epoxy resin derived from dimer acid, and the like. These may be used alone, or two or more may be used in any combination and mixing ratio.

Among these, from the viewpoint of fluidity of the composition, heat resistance, moisture absorption resistance, flame retardancy, and the like of the cured product, among the above epoxy resins, bisphenol A type epoxy resin, tetramethylbiphenol type epoxy resin and 4 , 4'-biphenol type epoxy resin, biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy resin and dihydroanthracene type epoxy resin, dicyclopentadiene type epoxy resin, orthocresol novolac type epoxy resin, trisphenol methane type epoxy resin Particularly preferred.
In the epoxy resin composition of this invention, when other epoxy resins mentioned later are contained, it is preferably 0.01 to 60 parts by weight with respect to 100 parts by weight of the total epoxy resin component. Further, it is more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less, particularly preferably 20 parts by weight or less, and more preferably 1 part by weight or more.

<Curing accelerator>
The epoxy resin composition of the present invention preferably contains a curing accelerator. By including a curing accelerator, the curing time can be shortened and the curing temperature can be lowered, and a desired cured product can be easily obtained.

The curing accelerator is not particularly limited, and specific examples include organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, and boron halide amine complexes.
Compounds that can be used as curing accelerators include triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, and tris (dialkylphenyl). ) Phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine Organic phosphines such as alkyldiarylphosphine, complexes of these organic phosphines with organic borons, and organic phosphines Maleic acid, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone And quinone compounds such as 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds formed by adding a compound such as diazophenylmethane.

Of the curing accelerators listed above, organic phosphines and phosphonium salts are preferred, and organic phosphines are most preferred. Moreover, only 1 type may be used for a hardening accelerator among the above-mentioned, and 2 or more types may be mixed and used for them in arbitrary combinations and ratios.
The curing accelerator is preferably used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy resin in the epoxy resin composition. More preferably, it is 0.5 parts by weight or more, further preferably 1 part by weight or more, more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less. When the content of the curing accelerator is not less than the above lower limit value, it is preferable for obtaining a curing accelerating effect. On the other hand, when the content is not more than the above upper limit value, desired cured physical properties are easily obtained.

<Inorganic filler>
An inorganic filler can be blended in the epoxy resin composition of the present invention. Examples of the inorganic filler include fused silica, crystalline silica, glass powder, alumina, calcium carbonate, calcium sulfate, talc, boron nitride and the like. Among these, when used for semiconductor sealing, a crushing type and / or spherical, fused and / or crystalline silica powder filler is preferable. By using an inorganic filler, when the epoxy resin composition is used as a semiconductor encapsulant, the thermal expansion coefficient of the semiconductor encapsulant can be brought close to the internal silicon chip or lead frame, and the semiconductor encapsulant can be used. Since the moisture absorption amount of the entire stopper can be reduced, the solder crack resistance can be improved. When using an inorganic filler in the epoxy resin composition of the present invention, it is preferable to blend 60 to 95% by weight of the entire epoxy resin composition.

When an inorganic filler is used in the epoxy resin composition of the present invention, the average particle size of the inorganic filler is usually 1 to 50 μm, preferably 1.5 to 40 μm, more preferably 2 to 30 μm. When the average particle size is not less than the above lower limit value, the melt viscosity is not excessively high and fluidity is not easily lowered, and when the average particle size is not more than the above upper limit value, a narrow gap in the mold is formed during molding. It is preferable because the filler is not easily clogged and the filling property of the material is easily improved.

<Release agent>
A mold release agent can be mix | blended with the epoxy resin composition containing the epoxy resin of this invention. As the release agent, for example, natural wax such as carnauba wax; synthetic wax such as polyethylene wax; higher fatty acids such as stearic acid and zinc stearate and metal salts thereof; and hydrocarbon release agents such as paraffin are appropriately blended. May be.
The amount of the release agent used in the epoxy resin composition of the present invention is preferably 0.1 to 5.0 parts by weight, more preferably 0.5 to 3.0 parts per 100 parts by weight of all epoxy resin components. Parts by weight. It is preferable for the amount of the release agent to be in the above range because good release properties can be exhibited while maintaining the curing characteristics of the epoxy resin composition.

<Coupling agent>
A coupling agent is preferably blended in the epoxy resin composition of the present invention. The silane coupling agent is preferably used in combination with an inorganic filler, and the adhesiveness between the epoxy resin as a matrix and the inorganic filler can be improved by blending the coupling agent. Examples of coupling agents include silane coupling agents and titanate coupling agents.

Examples of the silane coupling agent include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxy Aminosilane such as silane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysila And vinyl silanes such as γ-methacryloxypropyltrimethoxysilane, and epoxy, amino and vinyl polymer type silanes.

  Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate It is done.

  Any of these coupling agents may be used alone or in a combination of two or more in any combination and ratio. In addition, the compounding quantity of a coupling agent becomes like this. Preferably it is 0.1-3.0 weight part with respect to 100 weight part of all the epoxy resin components. If the blending amount of the coupling agent is equal to or more than the above lower limit value, the effect of improving the adhesion between the epoxy resin as a matrix and the inorganic filler due to the blending of the coupling agent tends to be improved. When the blending amount of the agent is not more than the above upper limit value, the coupling agent is less likely to bleed out from the resulting cured product.

<Other ingredients>
In the epoxy resin composition of the present invention, components other than those described above (may be referred to as “other components” in the present invention) can be blended. Examples of these various additives include flame retardants, plasticizers, reactive diluents, pigments, and the like, which can be appropriately blended as necessary. However, the epoxy resin composition of the present invention does not prevent any compounding other than the components listed above.

  Examples of the flame retardant include halogenated flame retardants such as brominated epoxy resins and brominated phenol resins, antimony compounds such as antimony trioxide, red flame retardants such as red phosphorus, phosphate esters and phosphines, melamine derivatives, etc. Nitrogen-based flame retardants, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide. The cured product of the epoxy resin composition of the present invention has excellent flame retardancy without the addition of a flame retardant.

[Cured product]
A cured product can be obtained by curing the epoxy resin composition of the present invention (hereinafter sometimes referred to as “cured product of the present invention”). Although it does not specifically limit about the method to harden | cure, Usually, hardened | cured material can be obtained by the thermosetting reaction by heating. The curing temperature is preferably selected as follows depending on the type of the curing agent. The specific temperature is usually 130 to 200 ° C. for a phenolic curing agent. Moreover, the curing temperature can be lowered by adding an accelerator to these curing agents. The reaction time is preferably 1 to 20 hours, more preferably 2 to 18 hours, and further preferably 3 to 15 hours. It is preferable for the reaction time to be not less than the above lower limit value because the curing reaction tends to proceed sufficiently. On the other hand, it is preferable for the reaction time to be less than or equal to the above upper limit value because it is easy to reduce deterioration due to heating and energy loss during heating.
The cured product of the present invention is excellent in blocking resistance, heat resistance, water absorption, and elastic modulus at high temperature. These measuring methods will be described in the following examples.

[Blocking resistance]
The epoxy resin composition of the present invention is excellent in blocking resistance, and preferably clears the test described below. A material having a problem with anti-blocking property is an important characteristic so as to be rejected even if it has excellent other characteristics. Moreover, since the handling property of a composition improves and production efficiency improves, it is preferable that blocking resistance is high.

〔Heat-resistant〕
The epoxy resin composition of the present invention has a glass transition temperature (Tg) of preferably 180 ° C. or higher. A higher glass transition temperature is preferable because thermal stress is less likely to be applied to the resin sealed when a semiconductor encapsulant is used, and defects such as passivation, chip damage, aluminum wiring slides, and package cracks are less likely to occur.

[Water absorption]
The epoxy resin composition of the present invention has a water absorption rate of preferably 1.53% or less. The lower the water absorption, the better the electrical reliability and the less the stress generated from the expansion of the water due to water absorption.

[Elastic modulus at high temperature]
The epoxy resin composition of the present invention has a high elastic modulus at a high temperature (250 ° C.), but preferably 100 MPa or more. The higher the modulus of elasticity at higher temperatures, the less likely the semiconductor package will be warped, and the better the adhesion between the encapsulant and the chip and the better the reliability.

[Use]
Since the epoxy resin composition of the present invention is excellent in heat resistance, water absorption, and elastic modulus at high temperature, it can be effectively used for any application as long as these physical properties are required. For this reason, paint fields such as electrodeposition paint for automobiles, heavy duty anti-corrosion paint for ships and bridges, paint for inner surface of beverage cans; laminated electronics, semiconductor encapsulant, insulating powder paint, electric and electronic for coil impregnation, etc. Field: Seismic reinforcement for bridges, concrete reinforcement, flooring for buildings, linings for water supply facilities, drainage / water-permeable pavement, civil / construction / adhesive fields for vehicle and aircraft adhesives, etc. be able to. Among these, it is particularly useful for the application of a semiconductor sealing material.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by the following example. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

<Manufacture of epoxy resin>
[Production Example 1]
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was charged with 251 parts of 4,4′-bis (chloromethyl) biphenyl, 3300 parts of hydroquinone, and 500 mL of methyl isobutyl ketone, and stirred at room temperature while blowing nitrogen. p-Toluenesulfonic acid (
(Monohydrate) 2.8 parts was added so that the liquid temperature did not exceed 50 ° C., and then heated to 110 ° C. and reacted for 2 hours. After completion of the reaction, 500 mL of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. After washing with water until the aqueous layer became neutral, the solvent was distilled off from the organic layer, and unreacted substances were removed by heating under reduced pressure to obtain a phenol resin with n = 0.06 in the formula (1).

[Production Example 2]
A phenol resin with n = 0.5 in formula (1) was obtained in the same manner except that the hydroquinone was changed to 495 parts in Production Example 1.
[Production Example 3]
A phenol resin of n = 0.7 in formula (1) was obtained in the same manner except that the hydroquinone was 420 parts in Production Example 1.

[Production Example 4]
A phenol resin of n = 0.9 in formula (1) was obtained in the same manner except that the amount of hydroquinone was 330 parts in Production Example 1.
[Production Example 5]
In Production Example 1, unreacted substances were removed under heating and reduced pressure, and then recrystallization was performed in methyl ethyl ketone. Thus, a phenol resin with n = 0 in formula (1) was obtained by the same method.

[Production Example 6]
A phenol resin having n = 0.2 in the following formula (2) was obtained by the same method except that resorcin was changed to 660 parts in Production Example 1.

[Example 1]
65 g of phenol resin (phenol resin represented by the formula (1) and n = 0.06) obtained in Production Example 1 in a 3 L four-neck flask equipped with a thermometer, a stirrer, and a condenser tube, 378 g of epichlorohydrin, isopropyl 221 g of alcohol and 60 g of water were charged, and the mixture was heated to 65 ° C. and dissolved uniformly. Then, 60 g of a 48.5 wt% aqueous sodium hydroxide solution was added dropwise over 90 minutes. After completion of the dropwise addition, the reaction was completed by holding at 65 ° C. for 30 minutes, and by-product salt and excess sodium hydroxide were removed by washing with water. Subsequently, excess epichlorohydrin and isopropyl alcohol were distilled off from the product under reduced pressure to obtain a crude epoxy resin. This crude epoxy resin was dissolved in 150 g of methyl isobutyl ketone, 2 g of a 48.5 wt% sodium hydroxide aqueous solution was added, and reacted again at a temperature of 65 ° C. for 1 hour. Thereafter, an aqueous sodium dihydrogen phosphate solution was added to the reaction solution to neutralize excess sodium hydroxide and washed with water to remove by-product salts. Next, methyl isobutyl ketone was completely removed under reduced pressure to obtain the desired epoxy resin.

[Example 2]
The target epoxy resin was obtained in the same manner as in Example 1 except that the phenol resin obtained in Production Example 2 (phenol resin represented by the formula (1) and n = 0.5) was used.
[Example 3]
The target epoxy resin was obtained in the same manner as in Example 1 except that the phenol resin obtained in Production Example 3 (phenol resin represented by formula (1) and n = 0.7) was used.

[Comparative Example 1]
The target epoxy resin was obtained in the same manner as in Example 1 except that the phenol resin obtained in Production Example 3 (phenol resin represented by the formula (1) and n = 0.9) was used.
[Comparative Example 2]
The target epoxy resin was obtained in the same manner as in Example 1 except that the phenol resin obtained in Production Example 4 (phenol resin represented by the formula (1) and n = 0) was used.

[Comparative Example 3]
The target epoxy resin was obtained in the same manner as in Example 1 except that the phenol resin obtained in Production Example 6 (phenol resin represented by formula (2) and n = 0.2) was used.
Examples 1 to 3 and Comparative Examples 1 to 3 The epoxy equivalents, melt viscosity (150 ° C.), hydrolyzable chlorine content, and softening point of the obtained epoxy resins were measured by the methods described above, and the results are shown in Table 1.

[Production and evaluation of epoxy resin composition]
[Examples 4 to 6 and Comparative Examples 4 to 6]
The epoxy resin and the curing agent were blended in the proportions shown in Table 2, heated to 100 ° C. and stirred until uniform. Then, it cooled to 80 degreeC, the hardening accelerator was added in the ratio shown in Table 2, and it stirred until it became uniform, and prepared the epoxy resin composition. In Table 2, “part” represents “part by weight”.

The used curing agents and curing accelerators are as follows.
Curing agent: phenol novolac resin (trade name PSM6200 manufactured by Gunei Chemical Co., Ltd. (hydroxyl equivalent: 103 g / equivalent))
Curing accelerator: Triphenylphosphine (trade name, triphenylphosphine, manufactured by Tokyo Chemical Industry Co., Ltd.)
Two glass plates each having a release pet film laminated thereon were prepared on one side, and these glass plates were provided with the release pet film side as an inner surface, and a glass plate interval was adjusted to 5 mm to prepare a casting plate.
An epoxy resin composition was cast on this casting plate and cured by heating at 120 ° C. for 2 hours and then at 175 ° C. for 6 hours to obtain a cured product.
The obtained cured product was evaluated as follows, and the results are shown in Table 2.

[Blocking test of composition]
In the formulation of Table 2, the epoxy resin and the curing agent were heated to 100 ° C. and stirred until uniform, and cooled at 5 ° C. for 30 minutes to obtain a composition. Thereafter, the product crushed with a hammer and passed through a 5 mm square mesh was put into a cylinder having a diameter of 5 cm and a length of 15 cm and left at 20 ° C. for 72 hours. After that, a product that passed a 1 cm square mesh was evaluated as ○ as a composition that did not block 50% or more, and a product that passed a 1 cm square mesh was evaluated as × as a composition that blocked 50% or less. .

[Measurement of glass transition temperature (Tg (E '')]
The cured product was cut into a length of 5 cm, a width of 1 cm, and a thickness of 5 mm to obtain a test piece. Analysis was performed by a thermomechanical analyzer (DMS: EXSTAR 6100 manufactured by Seiko Instruments Inc.) in the three-point bending mode by the following measurement method, and the peak top of E ″ at 1 Hz was defined as Tg (E ″).
(Measuring method)
First temperature increase: 5 ° C / min, 30 ° C to 280 ° C
[Measurement of water absorption]
The cured product was cut into a length of 3 cm, a width of 3 cm, and a thickness of 5 mm to obtain a test piece. A 168 hr test piece was placed in a constant temperature and humidity chamber adjusted to 85 ° C. and 85%, and the weight change rate due to the test piece supplying water was taken as the water absorption rate.

[Elastic modulus at high temperature (measurement of 250 ° C. (E ′)]
The cured product was cut into a length of 5 cm, a width of 1 cm, and a thickness of 5 mm to obtain a test piece. Analysis was performed by a thermomechanical analyzer (DMS: EXSTAR6100 manufactured by Seiko Instruments Inc.) in the three-point bending mode by the following measuring method, and 250 ° C. (E ′) of 1 Hz was defined as an elastic modulus at a high temperature.
(Measuring method)
First temperature increase: 5 ° C / min, 30 ° C to 280 ° C

[Evaluation of results]
From Table 1, Examples 1-3 which are the epoxy resins of this invention manufactured using the phenol resin whose n number of Formula (1) is in the regulation range of this invention are with respect to the epoxy resin of the comparative example 1, It can be seen that since the melt viscosity at 150 ° C. is excellent in handling property and hydrolyzable chlorine is low, the electrical properties are excellent.

Moreover, from Table 2, the epoxy resin hardened | cured material of Examples 4-6 using the epoxy resin of Examples 1-3 was excellent in heat resistance, water absorption, 250 compared with the epoxy resin hardened | cured material of the comparative example 3. It can be seen that it has high elasticity in a ℃ environment.
On the other hand, the epoxy resin of Comparative Example 2 has a lower softening point than the epoxy resins of Examples 1 to 3, and has a blocking problem. Moreover, although it mixed with the phenol resin in the comparative example 4 and the blocking test was implemented, compared with the epoxy resin composition of Examples 4-6, it is inferior in blocking resistance and is so serious on handling that it refuses actual use. There's a problem.

The epoxy resin of Comparative Example 3 has higher hydrolyzable chlorine than the epoxy resins of Examples 1 to 3. This is presumed to be derived from the skeleton. Moreover, it is inferior to blocking resistance compared with the epoxy resin composition of Examples 4-6, and is also poor in water absorption and the high elasticity in a 250 degreeC environment.
When these are put together, the epoxy resin of Examples 1-3 and the epoxy resin composition of Examples 4-6 are compared with the epoxy resin of Comparative Examples 1-3, and the epoxy resin composition of Comparative Examples 4-6. You can see that it is excellent.

Claims (10)

Following formula (1)

(In the above formula (1), n represents an average value and takes a value of 0.01 to 0.8.)
An epoxy resin obtained by converting a phenol resin represented by   The epoxy resin according to claim 1, which has an epoxy equivalent of 161 to 191 g / equivalent.   The epoxy resin according to claim 1, wherein the melt viscosity at 150 ° C. is 3.5 Pa · s or less.   The epoxy resin according to any one of claims 1 to 3, wherein the hydrolyzable chlorine is 770 ppm or less.   The epoxy resin according to any one of claims 1 to 4, which has a softening point of 48 to 70 ° C.   The epoxy resin composition which contains 0.01-1000 weight part of hardening | curing agents with respect to 100 weight part of epoxy resins in any one of Claim 1 to 5.   The epoxy resin composition according to claim 6, wherein the curing agent is at least one selected from the group consisting of a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, and an amide curing agent.   The epoxy resin composition according to claim 6 or 7, further comprising an epoxy resin different from the epoxy resin according to any one of claims 1 to 5.   Hardened | cured material formed by hardening | curing the epoxy resin composition in any one of Claim 6 to 8.   An electrical / electronic component obtained by curing the epoxy resin composition according to claim 6.